Coated oil and gas well production devices

Abstract

Provided are coated oil and gas well production devices and methods of making and using such coated devices. In one form, the coated oil and gas well production device includes an oil and gas well production device including one or more bodies, and a coating on at least a portion of the one or more bodies, wherein the coating is chosen from an amorphous alloy, a heat-treated electroless or electro plated based nickel-phosphorous composite with a phosphorous content greater than 12 wt %, graphite, MoS2, WS2, a fullerene based composite, a boride based cermet, a quasicrystalline material, a diamond based material, diamond-like-carbon (DLC), boron nitride, and combinations thereof. The coated oil and gas well production devices may provide for reduced friction, wear, corrosion, erosion, and deposits for well construction, completion and production of oil and gas.

1. A coated oil and as well production device comprising:
 an oil and gas well production device including one or more cylindrical bodies, and 
 a coating on at least a portion of the one or more cylindrical bodies, 
 wherein the coating is chosen from a fullerene based composite, diamond-like-carbon (DLC), and combinations thereof, 
 wherein the coefficient of friction of the coating is less than or equal to 0.15, and the coating provides a hardness greater than 1000 VHN. 
 
     
     
       2. The coated device of  claim 1 , wherein the one or more cylindrical bodies include two or more cylindrical bodies in relative motion to each other. 
     
     
       3. The coated device of  claim 1 , wherein the one or more cylindrical bodies are static relative to each other. 
     
     
       4. The coated device of  claim 1 , wherein the one or more cylindrical bodies include two or more radii. 
     
     
       5. The coated device of  claim 4 , wherein the one or more cylindrical bodies includes one or more cylindrical bodies substantially within one or more other cylindrical bodies. 
     
     
       6. The coated device of  claim 4 , wherein the two or more radii are of substantially the same dimensions or substantially different dimensions. 
     
     
       7. The coated device of  claim 4 , wherein the one or more cylindrical bodies are contiguous to each other. 
     
     
       8. The coated device of  claim 4 , wherein the one or more cylindrical bodies are not contiguous to each other. 
     
     
       9. The coated device of  claim 7  or  8 , wherein the one or more cylindrical bodies are coaxial or non-coaxial. 
     
     
       10. The coated device of  claim 9 , wherein the one or more cylindrical bodies have substantially parallel axes. 
     
     
       11. The coated device of  claim 9 , wherein the one or more non-coaxial cylindrical bodies are helical in inner surface, helical in outer surface or a combination thereof. 
     
     
       12. The coated device of  claim 1 , wherein the one or more cylindrical bodies are solid, hollow or a combination thereof. 
     
     
       13. The coated device of  claim 1 , wherein the one or more cylindrical bodies include at least one cylindrical body that is substantially circular, substantially elliptical, or substantially polygonal in outer cross-section, inner cross-section or inner and outer cross-section. 
     
     
       14. The coated device of  claim 1 , wherein the coefficient of friction of the coating is less than or equal to 0.10. 
     
     
       15. The coated device of  claim 1 , wherein the coating provides a hardness greater than 1500 VHN. 
     
     
       16. The coated device of  claim 1 , wherein the coating provides at least 3 times greater wear resistance than an uncoated device. 
     
     
       17. The coated device of  claim 1 , wherein the water contact angle of the coating is greater than 60 degrees. 
     
     
       18. The coated device of  claim 1 , wherein the coating provides a surface energy less than 1 J/m 2 . 
     
     
       19. The coated device of  claim 18 , wherein the coating provides a surface energy less than 0.1 J/m 2 . 
     
     
       20. The coated device of  claim 1 , wherein the coating comprises a single coating layer or two or more coating layers. 
     
     
       21. The coated device of  claim 20 , wherein the two or more coating layers are of substantially the same or different coatings. 
     
     
       22. The coated device of  claim 20 , wherein the thickness of the single coating layer and of each layer of the two or more coating layers range from 0.5 microns to 5000 microns. 
     
     
       23. The coated device of  claim 20 , wherein the coating further comprises one or more buffer layers. 
     
     
       24. The coated device of  claim 23 , wherein the one or more buffer layers are interposed between the surface of the one or more cylindrical bodies and the single coating layer or the two or more coating layers. 
     
     
       25. The coated device of  claim 23 , wherein the one or more buffer layers are chosen from elements, alloys, carbides, nitrides, carbo-nitrides, and oxides of the following:
 silicon, titanium, chromium, tungsten, tantalum, niobium, vanadium, zirconium, or hafnium. 
 
     
     
       26. The coated device of  claim 1 , wherein the dynamic friction coefficient of the coating is not lower than 50% of the static friction coefficient of the coating. 
     
     
       27. The coated device of  claim 1 , wherein the dynamic friction coefficient of the coating is greater than or equal to the static friction coefficient of the coating. 
     
     
       28. The coated device of  claim 1  , wherein the one or more cylindrical bodies further includes hardbanding on at least a portion thereof. 
     
     
       29. The coated device of  claim 28 , wherein the hardbanding comprises a cermet based material, a metal matrix composite or a hard metallic alloy. 
     
     
       30. The coated device of  claim 1  or  28  wherein the one or more cylindrical bodies further includes a buttering layer interposed between the surface of the one or more cylindrical bodies and the coating or hardbanding on at least a portion of the cylindrical bodies. 
     
     
       31. The coated device of  claim 30 , wherein the buttering layer comprises a stainless steel or a nickel based alloy. 
     
     
       32. The coated device of  claim 1 , wherein the one or more cylindrical bodies further include threads. 
     
     
       33. The coated device of  claim 32 , wherein at least a portion of the threads are coated. 
     
     
       34. The coated device of  claim 32  or  33 , further comprising a sealing surface, wherein at least a portion attic sealing surface is coated. 
     
     
       35. The coated device of any one of  claim 1 ,  2  or  3 , wherein the one or more cylindrical bodies are well construction devices. 
     
     
       36. The coated device of  claim 34 , wherein the well construction devices are chosen from drill stem, casing, tithing string, wireline/braided line/multi-conductor/single conductor/slickline; coiled tubing, vaned rotors and stators of Moyno™ and progressive cavity pumps, expandable tubulars, expansion mandrels, centralizers, contact rings, wash pipes, shaker screens for solids control, overshot and grapple, marine risers, surface flow lines, and combinations thereof. 
     
     
       37. The coated device of any one of  claim 1 ,  2  or  3 , wherein the one or more cylindrical bodies are completion and production devices. 
     
     
       38. The coated device of  claim 36 , wherein the completion and production devices are chosen from plunger lifts; completion sliding sleeve assemblies; coiled tubing; sucker rods; Corods™; tubing string; pumping jacks; stuffing boxes; packoffs and lubricators; pistons and piston liners; vaned rotors and stators of Moyno™ and progressive cavity pumps; expandable tubulars; expansion mandrels; control lines and conduits; tools operated in well bores; wireline/braided line/multi-conductor/single conductor/slickline; centralizers; contact rings; perforated basepipe; slotted basepipe; screen basepipe for sand control; wash pipes; shunt tubes; service tools used in gravel pack operations; blast joints; sand screens disposed within completion intervals; Mazeflo™ completion screens; sintered screens; wirewrap screens; shaker screens for solids control; overshot and grapple; marine risers; surface flow lines, stimulation treatment lines, and combination thereof. 
     
     
       39. A coated oil and gas well production device comprising:
 an oil and gas well production device including one or more bodies with the proviso that the one or more bodies does not include a drill bit, and 
 a coating on at least a portion of the one or more bodies, 
 wherein the coating is chosen from a fullerne based composite, diamond-like-carbon (DLC), and combinations thereof, 
 wherein the coefficient of friction of the coating is less than or equal to 0.15, and the coating provides a hardness greater than 1000 VHN. 
 
     
     
       40. The coated device of  claim 39 , wherein the one or more bodies include two or more bodies in relative motion to each other. 
     
     
       41. The coated device of clams  39 , wherein the one or more bodies are static relative to each other. 
     
     
       42. The coated device of clams  39 , Therein the one or more bodies include spheres and complex geometries. 
     
     
       43. The coated device of  claim 42 , wherein the complex geometries have at least a portion that is non-cylindrical in shape. 
     
     
       44. The coated device of  claim 43 , wherein the one or more bodies include one or more bodies substantially within one or more other bodies. 
     
     
       45. The coated device of  claim 39 , wherein the one or more bodies are contiguous to each other. 
     
     
       46. The coated device of  claim 39 , wherein the one or more bodies are not contiguous to each other. 
     
     
       47. The coated device of  claim 45  or  46 , wherein the one or more bodies are coaxial or non-coaxial. 
     
     
       48. The coated device of  claim 39 , wherein the one or more bodies are solid, hollow or a combination thereof. 
     
     
       49. The coated device of  claim 39 , wherein the one or more bodies include at least one body that is substantially circular, substantially elliptical, or substantially polygonal in outer cross-section, inner cross-section or inner and outer cross-section. 
     
     
       50. The coated device of  claim 39 , wherein the coefficient of friction of the coating is less than or equal to 0.10. 
     
     
       51. The coated device of  claim 39 , wherein the coating provides a hardness greater than 1500 VHN. 
     
     
       52. The coated device of  claim 39 , wherein the coating provides at least 3 times greater wear resistance than an uncoated device. 
     
     
       53. The coated device of  claim 39 , wherein the water contact angle of the coating is greater than 60 degrees. 
     
     
       54. The coated device of  claim 39 , wherein the coating provides a surface energy less than 1 J/m 2 . 
     
     
       55. The coated device of  claim 54 , wherein the coating provides a surface energy less than 0.1 J/m 2 . 
     
     
       56. The coated device of  claim 39 , wherein the coating comprises a single coating layer or two or more coating layers. 
     
     
       57. The coated device of  claim 56 , wherein the two or more coating layers are of substantially the same or different coatings. 
     
     
       58. The coated device of  claim 56 , wherein the thickness of the single coating layer and of each layer of the two or more coating layers range from 0.5 microns to 5000 microns. 
     
     
       59. The coated device of  claim 56 , wherein the coating further comprises one or more buffer layers. 
     
     
       60. The coated device of  claim 59 , wherein the one or more buffer layers are interposed between the surface of the one or more cylindrical bodies and the single coating layer or the two or more coating layers. 
     
     
       61. The coated device of  claim 59 , wherein the one or more buffer layers are chosen from elements, alloys, carbides, nitrides, carbo-nitrides, and oxides of the following: silicon, titanium, chromium, tungsten, tantalum, niobium, vanadium, zirconium, or hafnium. 
     
     
       62. The coated device of  claim 39 , wherein the dynamic friction coefficient of the coating is not lower than 50% of the static friction coefficient of the coating. 
     
     
       63. The coated device of  claim 39 , wherein the dynamic friction coefficient of the coating is greater than or equal to the static friction coefficient of the coating. 
     
     
       64. The coated device of  claim 39 , wherein the one or more bodies further includes hardbanding on at least a portion thereof. 
     
     
       65. The coated device of  claim 64 , wherein the hardbanding comprises a cermet based material, a metal matrix composite or a hard metallic alloy. 
     
     
       66. The coated device of  claim 39  or  64  wherein the one or more bodies further includes a buttering layer interposed between the surface of the one or more bodies and the coating or hardbanding on at least a portion of the bodies. 
     
     
       67. The coated device of  claim 66 , wherein the buttering layer comprises a stainless steel or a nickel based alloy. 
     
     
       68. The coated device of  claim 39 , wherein the one or more bodies firth include threads. 
     
     
       69. The coated device of  claim 68 , wherein at least a portion of the threads are coated. 
     
     
       70. The coated device of  claim 68  or  69 , further comprising a sealing surface, wherein at least a portion of the sealing surface is coated. 
     
     
       71. The coated device of any one of  claim 39 ,  40  or  41 , wherein the one or more bodies are well construction devices. 
     
     
       72. The coated device of  claim 71 , wherein the well construction devices are chosen from chokes, valves, valve seats, nipples, ball valves, annular isolation valves, subsurface safety valves, centrifuges, elbows, tees, couplings, blowout preventers, wear bushings, dynamic metal-to-metal seals in reciprocating and/or rotating seals assemblies, springs in safety valves, shock subs, and jar, logging tool arms, rig skidding equipment, pallets, and combinations thereof. 
     
     
       73. The coated device of any one of  claim 39 ,  40  or  41 , wherein the one or more bodies are completion and production devices. 
     
     
       74. The coated device of  claim 73 , wherein the completion and production devices are chosen from chokes, valves, valve seats, nipples, ball valves, inflow control devices, smart well valves, annular isolation valves, subsurface safety valves, centrifuges, gas lift and chemical injection valves, elbows, tees, couplings, blowout preventers, wear bushings, dynamic metal-to-metal seals in reciprocating and/or rotating seals assemblies, springs in safety valves, shock subs, and jar, logging tool arms, sidepockets, mandrels, packer slips, packer latches, sand probes, wellstream gauges, and combinations thereof. 
     
     
       75. A method for coating an oil and gas well production device comprising:
 providing a coated oil and gas well production device comprising an oil and gas well production device including one or more cylindrical bodies, and 
 a coating on at east a portion of the one or more cylindrical bodies, 
 wherein the coating is chosen from a fullerene based composite, diamond-like-carbon (DLC), and combinations thereof, 
 wherein the coefficient of friction of the coating is less than or equal to 0.15, and the coating provides a hardness greater than 1000 VHN, and 
 utilizing the coated oil and gas well production device in well construction, completion, or production operations. 
 
     
     
       76. The method of  claim 75 , wherein the one or more cylindrical bodies include two or more cylindrical bodies in relative motion to each other. 
     
     
       77. The method of  claim 75 , wherein the one or more cylindrical bodies are static relative to each other. 
     
     
       78. The method of  claim 75 , wherein the one or more cylindrical bodies include two or more radii. 
     
     
       79. The method of  claim 78 , wherein the one or more cylindrical bodies includes one or more cylindrical bodies substantially within one or more other cylindrical bodies. 
     
     
       80. The method of  claim 78 , wherein the two or more radii are of substantially the same dimensions or substantially different dimensions. 
     
     
       81. The method of  claim 78 , wherein the one or more cylindrical bodies are contiguous to each other. 
     
     
       82. The method of  claim 78 , wherein the one or more cylindrical bodies are not contiguous to each other. 
     
     
       83. The method of  claim 81  or  82 , wherein the one or more cylindrical bodies are coaxial or non-coaxial. 
     
     
       84. The method of  claim 83 , wherein the one or more non-coaxial cylindrical bodies have substantially parallel axes. 
     
     
       85. The method of  claim 83 , wherein the one or more non-coaxial cylindrical bodies are helical in inner surface, helical in outer surface or a combination thereof. 
     
     
       86. The method of  claim 75 , wherein the one or more cylindrical bodies are solid, hollow or a combination thereof. 
     
     
       87. The method of  claim 75 , wherein the one or more cylindrical bodies include at least one cylindrical body that is substantially circular, substantially elliptical, or substantially polygonal in outer cross-section, inner cross-section or inner and outer cross-section. 
     
     
       88. The method of  claim 75 , wherein the coefficient of friction of the coating is less than or equal to 0.10. 
     
     
       89. The method of  claim 75 , wherein the coating provides at least 3 times greater wear resistance than an uncoated device. 
     
     
       90. The method of  claim 75 , wherein the water contact angle of the coating is greater than 60 degrees. 
     
     
       91. The method of  claim 75 , wherein the coating provides a surface energy less than 1 J/m 2 . 
     
     
       92. The method of  claim 75 , wherein the coating comprises a single coating layer or two or more coating layers. 
     
     
       93. The method of  claim 92 , wherein the two or more coating layers are of substantially the same or different coatings. 
     
     
       94. The method of  claim 92 , wherein the thickness of the single coating layer and of each layer of the two or more coating layers range from 0.5 microns to 5000 microns. 
     
     
       95. The method of  claim 92 , wherein the coating further comprises one or more buffer layers. 
     
     
       96. The method of  claim 95 , wherein the one or more buffer layers are interposed between the surface of the one or more cylindrical bodies and the single coating layer or the two or more coating layers. 
     
     
       97. The method of  claim 95 , wherein the one or more buffer layers are chosen from elements, alloys, carbides, nitrides, carbo-nitrides, and oxides of the following: titanium, chromium, tungsten, tantalum, niobium, vanadium, zirconium, or hafnium. 
     
     
       98. The method of  claim 75 , wherein the dynamic friction coefficient of the coating is not lower than 50% of the static friction coefficient of the coating. 
     
     
       99. The method of  claim 75 , wherein the dynamic friction coefficient of the coating is greater than or equal to the static friction coefficient of the coating. 
     
     
       100. The method of  claim 75 , wherein the one or more cylindrical bodies further includes hardbanding on at least a portion thereof. 
     
     
       101. The method of  claim 100 , wherein the hardbanding comprises a cermet based material, a metal matrix composite or a hard metallic alloy. 
     
     
       102. The method of  claim 75  or  100 , wherein the one or more cylindrical bodies further includes a buttering layer interposed between the surface of the one or more cylindrical bodies and the coating or hardbanding on at least a portion of the cylindrical bodies. 
     
     
       103. The method of  claim 102 , wherein the buttering layer comprises a stainless steel or a nickel based alloy. 
     
     
       104. The method of  claim 75 , wherein the one or more cylindrical bodies further include threads. 
     
     
       105. The method of  claim 104 , wherein at least a portion of the threads are coated. 
     
     
       106. The method of  claim 104  or  105 , further comprising a sealing surface, wherein at least a portion of the sealing surface is coated. 
     
     
       107. The method of any one of  claim 75 ,  76 , or  77 , wherein the one or more cylindrical bodies are well construction devices. 
     
     
       108. The method of  claim 107 , wherein the well construction devices are chosen from drill stem, casing, tubing string, wireline/braided line/multi-conductor/single conductor/slickline; coiled tubing, vaned rotors and stators of Moyno™ and progressive cavity pumps, expandable tubulars, expansion mandrels, centralizers, contact rings, wash pipes, shaker screens fur solids control, overshot and grapple, marine risers, surface flow lines, and combinations thereof. 
     
     
       109. The method of any one of  claim 75 ,  76 , or  77 , wherein the one or more cylindrical bodies are completion and production devices. 
     
     
       110. The method of  claim 109 , wherein the completion and production devices are chosen from plunger lifts; completion sliding sleeve assemblies; coiled tubing; sucker rods; Corods™; tubing string; pumping jacks; stuffing boxes; packoffs and lubricators; pistons and piston liners; vaned rotors and stators of Moyno™ and progressive cavity pumps; expandable tubulars; expansion mandrels; control lines and conduits; tools operated in well bores; wireline/braided line/multi-conductor/single conductor/slickline; centralizers; contact rings; perforated basepipe; slotted basepipe; screen basepipe for sand control; wash pipes; shunt tubes; service tools used in gravel pack operations; blast joints; sand screens disposed within completion intervals; Mazeflo™ completion screens; sintered screens; wirewrap screens; shaker screens tier solids control; overshot and grapple; marine risers; surface flow lines, stimulation treatment lines, and combination thereof. 
     
     
       111. The method of  claim 75 , wherein the diamond-like-carbon (DLC) is applied by physical vapor deposition, chemical vapor deposition, or plasma assisted chemical vapor deposition coating techniques. 
     
     
       112. The method of  claim 111 , wherein the physical vapor deposition coating method is chosen from RF-DC plasma reactive magnetron sputtering, ion beam assisted deposition, cathodic arc deposition and pulsed laser deposition. 
     
     
       113. A method for coating an oil and gas well production device comprising:
 providing an oil and gas well production device including one or more bodies with the proviso that the one or more bodies does not include a drill hit, and 
 a coating on at least a portion of the one or more bodies, 
 wherein the coating is chosen from a fullerene based composite, diamond-like-carbon (DLC), and combinations thereof, 
 wherein the coefficient of friction of the coating is less than or equal to 0.15, and the coating provides a hardness greater than 1000 VHN, and 
 utilizing the coated oil and gas well production device in well construction, completion, or production operations. 
 
     
     
       114. The method of  claim 113 , wherein the one or more bodies include two or more bodies in relative motion to each other. 
     
     
       115. The method of  claim 113 , wherein the one or more bodies are static relative to each other. 
     
     
       116. The method of  claim 113 , wherein the one or more bodies include spheres or complex geometries. 
     
     
       117. The method of  claim 116 , wherein the complex geometries have at least a portion that is non-cylindrical in shape. 
     
     
       118. The method of  claim 114  or  115 , wherein the one or more bodies include one or more bodies substantially within one or more other bodies. 
     
     
       119. The method of  claim 114  or  115 , wherein the one or more bodies are contiguous to each other. 
     
     
       120. The method of  claim 114  or  115 , wherein the one or more bodies are not contiguous to each other. 
     
     
       121. The method of  claim 114  or  115 , wherein the one or more bodies are coaxial or non-coaxial. 
     
     
       122. The method of  claim 113 , wherein the one or more bodies are solid, hollow or a combination thereof. 
     
     
       123. The method of  claim 113 , wherein the one or more bodies include at least one body that is substantially circular, substantially elliptical, or substantially polygonal in outer cross-section, inner cross-section or inner and outer cross-section. 
     
     
       124. The method of  claim 113 , wherein the coefficient of friction of the coating is less than or equal to 0.10. 
     
     
       125. The method of  claim 113 , wherein the coating provides at least 3 times greater wear resistance than an uncoated device. 
     
     
       126. The method of  claim 113 , wherein the water contact angle of the coating is greater than 60 degrees. 
     
     
       127. The method of  claim 113 , wherein the coating provides a surface energy less than 1 J/m 2 . 
     
     
       128. The coated device of  claim 113 , wherein the coating comprises a single coating layer or two or more coating layers. 
     
     
       129. The method of  claim 128 , wherein the two or more coating layers are of substantially the same or different coatings. 
     
     
       130. The method of  claim 128 , wherein the thickness of the single coating layer and of each layer of the two or more coating layers range from 0.5 microns to 5000 microns. 
     
     
       131. The method of  claim 128 , wherein the coating further comprises one or more buffer layers. 
     
     
       132. The method of  claim 131 , wherein the one or more buffer layers are interposed between the surface of the one or more cylindrical bodies and the single coating layer or the two or more coating layers. 
     
     
       133. The method of  claim 131 , wherein the one or more buffer layers are chosen from elements, alloys, carbides, nitrides, carbo-nitrides, and oxides of the following: silicon, titanium, chromium, tungsten, tantalum, niobium, vanadium, zirconium, or hafnium. 
     
     
       134. The method of  claim 113 , wherein the dynamic friction coefficient of the coating is not lower than 50% of the static friction coefficient of the coating. 
     
     
       135. The method of  claim 113 , wherein the dynamic friction coefficient of the coating is greater than or equal to the static friction coefficient of the coating. 
     
     
       136. The method of  claim 113 , wherein the one or more bodies further includes hardbanding on at least a portion thereof. 
     
     
       137. The method of  claim 136 , wherein the hardbanding comprises a cermet based material, a metal matrix composite or a hard metallic alloy. 
     
     
       138. The method of  claim 113  or  136  wherein the one or more bodies further includes a buttering layer interposed between the surface of the one or more bodies and the coating or hardbanding on at least a portion of the bodies. 
     
     
       139. The method of  claim 138 , wherein the buttering layer comprises a stainless steel or a nickel based alloy. 
     
     
       140. The method of  claim 113 , wherein the one or more bodies further include threads. 
     
     
       141. The method of  claim 140 , wherein at least a portion of the threads are coated. 
     
     
       142. The method of  claim 140  or  141 , further comprising a sealing surface, wherein at least a portion of the sealing surface is coated. 
     
     
       143. The method of any one of  claim 113 ,  114 , or  115 , wherein the one or more bodies are well construction devices. 
     
     
       144. The method of  claim 143 , wherein the well construction devices are chosen from chokes, valves, valve seats, nipples, ball valves, annular isolation valves, subsurface safety valves, centrifuges, elbows, tees, couplings, blowout preventers, wear bushings, dynamic metal-to-metal seals in reciprocating and/or rotating seals assemblies, springs in safety valves, shock subs, and jar, logging tool arms, rig skidding equipment, pallets, and combinations thereof. 
     
     
       145. The method of any one of  claim 113 ,  114 , or  115 , wherein the one or more bodies are completion and production devices. 
     
     
       146. The method of  claim 145 , wherein the completion and production devices are chosen from chokes, valves, valve seats, nipples, ball valves, inflow control devices, smart well valves, annular isolation valves, subsurface safety valves, centrifuges, gas lift and chemical injection valves, elbows, tees, couplings, blowout preventers, wear bushings, dynamic metal-to-metal seals in reciprocating and/or rotating seals assemblies, springs in safety valves, shock subs, and jar, logging tool arms, sidepockets, mandrels, packer slips, packer latches, sand probes, wellstream gauges, and combinations thereof. 
     
     
       147. The method of  claim 113 , wherein the diamond-like-carbon (DLC) is applied by physical vapor deposition, chemical vapor deposition, or plasma assisted chemical vapor deposition coating techniques. 
     
     
       148. The method of  claim 147 , wherein the physical vapor deposition coating method is chosen from RF-DC plasma reactive magnetron sputtering, ion beam assisted deposition, cathodic arc deposition and pulsed laser deposition.